Solvent extraction process applied to feed stocks of high boiling points



H. S. BLOCH SOLVENT EXTRAGTION PROCESS APPLIED TO FEED March 19, 1957 STOCKS OF HIGH BOILING POINTS Filed Aug. 20, 1952 www All

INVENTORZ HERMAN s. ,BLOCH BY:

mJa/Mwi ATTORNE Si mzoN SOLVENT EXTRACTIN PROCESS APPLIED TO FEED STOCKS F HIGH BOILING POINTS Herman S. Bloch, Chicago, lll., assigner to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Appricaesa August zo, 1952, serial No. 305,520

4 Claims. (Cl. 260-674) This invention relates to a liquid-liquid extraction process for separating a mixture of organic compounds of relatively high boiling points utilizing a selective solvent for one or more `components of the mixture preferentially miscible with the solvent. In one of its preferred specific applications, the process of the present invention concerns a separation process for the recovery of a polycyclic or high boiling alkyl aromatic hydrocarbon from a hydrocarbon mixture containing the same and utilizing a selective solvent for the aromatic hydrocarbon components of the feed stock, said extracted compound being recovered from the extract stream by displacement with a lower boiling, preferentially soluble polar compound.

The method of separation provided herein is essentially a liquid-liquid phase contacting process, preferably etfected under countercurrent ow conditions, wherein a liquid solvent, generally an oxygen-containing or nitrogen-containing organic compound which selectively dissolves only one or less than all of the components of the feed stock mixtureis contacted under binary phase mixing conditions with the feed stock to form distinct and separable phases, one of which is a rich solvent or extract phase containing the feed stock component or components selectively soluble in said solvent and the other a raffinate phase comprising the components rejected by the solvent and less readily dissolved therein. In accordance with conventional countercurrent extraction practice, the extract containing stream is separately treated, generally by heating or steam stripping the same, to recover the feed stock component dissolved in the solvent. It isevident that such Asolvent extraction method of recovery, although applicable to feed stock mixtures having boiling points below the boiling temperature or decomposition point of the solvent, may not generally be applied to feed stocks which boil above the boiling point of the solvent, and may only be applied to feeds which boil above the decomposition temperature of the solvent by use of distillation or stripping under vacuum or by other equally uneconomical procedures. The alternative procedure of stripping the solvent from the extract, although widely employed, is not economically attractive, especially when ,high solvent to extract ratios must be employed. The present method of separation, although a liquid-liquid solvent extraction process, is nevertheless applicable generally to the separation of feed stocks of relatively high boiling points and particularly to feed stocks which boilfat a temperature above 'the boiling point of the solvent or above its thermal stability point. The principal object of the invention, therefore, is to provide a liquid-liquid extraction procedure for the treatment of high boiling feed stock mixtures to separate one or morecomponents therefrom which are selectively soluble in the slovent extractant. Another object of the invention is to remove and recover substantially all of the relatively 'polar organic feed stock component or components of a mixture of prganic compounds in a high state of purity` er in a connited States Patent O M' 2,786,085 Patented Mar. 19, 1957 centration greater than is present in the initial feed stock mixture.

In one of its embodiments, the present invention concerns a process for separating a polar organic compound A from a mixture thereof with a less polar organic cornpound B of substantially the same volatility which comprises contacting said mixture with a liquid solvent which selectively dissolves said compound A, forming thereby an extract phase comprising said compound A and said solvent, separating saidextract phase from a resulting primary raffinate comprising said compound B, separately contacting said extract phase with a polar organic compound C which is more volatile with respect to and separable from said solvent and said compound A, thereby effecting the displacement of said compound A from said extract phase, separating a resulting secondary raffinate stream comprising compound A displaced into an excess of said compound C and a secondary extract phase comprising said compound C and said solvent, thereafter subjecting said secondary raffinate stream to distillation whereby said compound A is segregated from said cornpound C, and separately stripping compound C from said secondary extract phase to recover the solvent.

Another embodiment of the invention relates to a process for separating a polycyclic aromatic hydrocarbon rom a non-aromatic hydrocarbon of approximately the. same volatility which comprises contacting a mixture of said aromatic and non-aromatic hydrocarbons at a temperature of from about to about 200 C. with an aqueous solution of at least one oxy-polyalkylene glycol in which said polycyclic aromatic hydrocarbon is selectively soluble, separating a resulting extract stream comprising said glycol and containing dissolved therein said polycyclic aromatic hydrocarbon from a resulting primary ranate stream comprising non-aromatic hydrocarbon components of said mixture, separately contacting said extract stream with benzene, separating a resulting secondary raflinate stream comprising said polycyclic aromatic hydrocrabon dissolved in said benzene from a secondary extract stream, subjecting said secondary extract stream to distillation, separately recoveringregenerated solvent and a benzene stream, recycling said regenerated solvent to said first-mentioned contacting step and said benzene to said last-mentioned contacting step, subjecting said secondary raflinate stream to distillation and separately recovering therefrom benzene and said polycyclic aromatic hydrocarbon.

Suitable feed stock mixtures which may be subjected to the-present selective solvent extraction process include generally mixtures of organic compounds containing at least one component selectively soluble in the solvent charged to the process and characterized herein as a relatively polar organic compound A having a relatively high boiling point, usually above about C. Relatively polar organic compounds characterizing the components of the feed stock mixture selectively soluble in the liquid solvent composition provided in the present process are characterized generally as being relatively more polar than the components of the feed stock mixture rejected by the solvent, although solubility and extractability of any particular feed stock component in the solvent is not necessarily strictly correlated` with the `dipolemornent of the compound selectively soluble in and extracted by the-solvent.` For purposes of the present invention, thepolarity of an organic compound is considered to be equivalent to solubility in the selective solvent provided in the extraction stage of the process. In general, polarity is characterized by the relatively greater tendency of the comor associations with other organic compounds. in an organic compound generally accompanies the presmembers of the group A compounds, is believed to associatey itself with the solvent in a state knownY as a complex more readily than do other, less polar and less readily extracted components'. Y A y, t

The relatively high solubility ofl aromatic hydrocarbons as compared with other hydrocarbon types of like boiling range is illustrative of the second criterion by which the more soluble A compounds may be designated-namely, that their carbon:hydrogen ratio is greater than that of the less extractablematerials of like boiling range. Thus,

in a'narrow boiling fraction of mixed hydrocarbons, aro-l matics are more soluble than dienes, cycloolefins and acetylenes; dienes, cycloolefins and acetylenes more soluble than mono-olens and naphthenes; and mono-olefins and naphthenes more soluble than paraftins. ln general, unsaturated compounds are more soluble than saturated materials of the sameV carbonzhydrogen ratio, the unsaturation lending a degree of polarity which tends to Y increase the solubility; thus a mono-olefin is more soluble than a monocyclic cycloparaffn hydrocarbon of like boiling range.

In accordance with the above criteria, it is seen that more highly unsaturated glycerides occurring in vegetable or` animal` oils may be selectively dissolved from less unsaturated fatty glycerides, leading to a useful molecular segregation whereby, for example, a semi-drying oil may be converted to an extract comprisinga fast drying oil anda raffinate of substantially more saturatedcharacter thanthe feed, suitable for edible purposes.

Although the extractability of aV particular component of thefeed stock mixture is believed to be correlated generally'withits polarity or its. carbonzhydrogen ratio, it is not-intended to restrict the typesv of organic compounds suitable` as feedstocks to the solvent extraction process by such denitiomthe feed stock'mixture in any event comprising a mixture of at least one compound A more soluble inthesolvent Vthan the remaining components of the mixture designated as members of the group B compounds.

Y. Y The selective solvent extractionprocessfof this inventionnrnayvr beappliedto various mixtures of organic compoundsicontainingrone or more polar organic components vandisapplicable-.to a variety of mixtures of polar organic compounds. Thus, for example, the process may be utilizedfor the -segregationof high Vmolecular weight mer- Y captans, alkyl sulfides and -dialkyl Vsuldes from hydro- Vcar-bon mixturesfsuch asrelatively high boiling'petroleum fractions represented, for example, by a gas oil fraction boiling from about'200fto'about 350' C., lubricating oil fractions generally boiling above 300 C. or to the produ-cts of aA Fischer-Tropsch reaction which` may contain such polar components vas alcohols, ketones, and aldehydes. VThe process Vis also useful for the recovery of polycyclic aromatic phenols such as the'naph'thols from hydrocarbon fractions; for the separatiorrof the mixture of products of high molecularweight'hydrocarbon oxidation reactions, the products ofV which may contain one or more carboxyl, carbonyl or hydroxyl groups per molecule; for the extraction of polycyclic aromatic vhydrocarbons such as: naphthalene, anthracene, phenanthrene and their alkylV derivatives `from lubricatingY oil -fractions of petroleum; for the separation of aromatic `(i. e. smoking) components from kerosenes to be used for lighting purposes; for the removal of asphaltenes and other carbongenerating components from hydrocarbon feed stocks for catalytic conversions such as catalytic cracking; and for the extraction ofunsaturated fatty acids or their glyceride esters from the saturated acids or esters. Typical hydrocarbon mixtures utilizable as one type of feed stock in the present extraction procedure include distillate fractions of catalytically'cracked.petroleum, coal tar distillate fractions, specific boiling range fractions of straight-run petroleum distillates and narrow or Wide boiling range fractions of certain reformed or hydroformed petroleum fractions which are generally relatively rich in aromatic hydrocarbonsk and are a particularly suitable source of polycyclic and alkyl aromatic hydrocarbons. Y

The feed stock mixture of separable organic components may be subjected to continuous solvent extraction with'the solvents herein provided most advantageously in a countercurrent liquid-liquid contacting procedure, although co-current flow of solvent 'and the feed stock may likewise be adapted to the present process. In the preferred countercurrent method of operation, the solvent is introduced near one end of an extraction zone such as a vertical,.,elongated column, usually the uppermost end of the zone, since the solvent is usually the phase of greatestv density present within the extraction column, from which end a raffinate stream comprising rejected or non-extracted class B compounds of the feed stock mixture is also removed. The liquid feed stock is introduced at a point in the extraction column below theralinate outlet near the opposite end of the column. An extract phase or fat solvent stream comprising substantially all of the solvent and containing dissolvedtherein the extracted, relatively polar` class A component of the feedstock mixture is removed from the opposite end of the column below the point of entry for the feed stock in the embodiment Vin which the solvent is the phase of greatest density. The stream of extract is thereafter separately treated inaccordance with the succeeding stages of the present process, as hereinafter described.

Y The selective solvent-extractant,employed in the present separation process may be arsin'gle component liquid of anl organic compoundcapable of dissolving a substantial quantity of the polar A component of the feed stock, a mixture of two or more Vorganic components of this type capable of dissolving components from the feed stock mixture and preferentially'the relatively polar A components thereof, or a mixture of such organic primary solvents with a secondary solvent component which increaseslthe selectivity of the solvent composition for dissolving the polar A component of the feed stock. The presence of the secondary solvent constituent reduces the tendency of the ratinate B components to dissolve in the solvent stream and thus increases` the capacity of the solvent to reject these non-polar components of the feed stock mixture when contacted therewith in the primary extraction stage of the process. f

Organic compounds `which preferentially dissolve at least one of the A compounds of the feed stock may be of any particular compositionsuitable for this purpose, but organic compounds characterized as oxygen-containing or nitrogen-containing organic compounds are particularly suitable in their liquid state as selective solvents in the present process. These compounds, alsodesignated as the primary solventY component, maybe selected from such classes of compounds as-the aliphatic and cyclic alcohols, the, glycol ethers. (also referred to as polya'lkylene Y glycols) :as well Vas the glycolesters and glycol ether esters.

ln addition, certain other classes of compounds such as the ketones and theV nitriles, particularly the oxynitriley ethers also constituteja particularly-'preferred class of constituents be mutually soluble.

andthe mond, diand tri-butylene glycols. Certain glycol' ethers, such as the Cellosolve series of compounds (defined structurally as the allyl ethers of ethylene glycol) and including methyl, ethyl, propyl, and butylcellosolve are also effective solvents in the process. The Carbitols (defined structurally as thealkyl ethers of diethylene glycol) such as the methyl, ethyl, propyl, and butylcarbitols; the glycol and polyoxypoly-alkylene glycol esters of low molecular weight organic acids such as the acetates and propionates; the higher alcohols, such as caproyl alcohol, 2-ethylhexanol, lauryl alcohol, and the like; certain cyclic alcohols such as cyclo-pentanol, cyclo-hexanol, etc.; phenols and alkylphenols such as phenol itself, resorcinol, pyrocatechol, the various cresols, thymol etc.; the organic acid esters, such as the fatty acid esters of aliphatic alcohols; and thel cyano ethers, such as ,oxydipropio nitriles, ;86thiodipropionitrile and other typical representative compounds of the above series of compounds comprise an effective group of solvents. In the preferred method of recovering the dissolved solute components from the extract phase removed from the solute exchange zone of the present process, the solvent is stripped of the remaining dissolved solute by introducing a vapor such las steam, to remove substantially completely the last traces of dissolved solute. For this purpose, it is generally preferred to utilize a selective solvent composition containing a solvent component having a relatively high boiling point and low vapor pressure, the composition thereby remaining substantially in liquid phase when the fat solvent or extract phase is subjected to stripping in a succeeding stage of the process.

In order to increase the selectivity of the solvent for vthe desired A compound to be extracted from the feed irstock mixture, the solvent preferably contains a second- ,ary solvent component which reduces the solubility of :the rainate or B components in the solvent without materially affecting the solubility of the desired A component to be recovered in the process. The secondary :solvent component may also be useful for the specic jpurpose of providing a stripping agent in the solvent stripping stage of the process by selecting a secondary :solvent capable of vaporizing from the stripping zone as a side stream, the vapors being introduced in a heated state into the lower portion of the stripping column where the sensible heat of the vapors volatilizes the last traces of extracted solute from the rich solvent stream. Since the solvent composition supplied to the extraction zone is desirably a homogeneous solution of the primary and secondary solvent constituents, it is essential that these Normally liquid compounds possessing these properties, and as such suitable for use as the secondary solvent constituent, are such materials as water, furan, furfurol, furfuryl alcohol, low molecular weight esters such as methyl acetate, ethyl acetate, methyl lactate, and the like, the nitro-parans and their halogen-substituted analogs of low molecular weight such as nitromethane, nitroethane, di-nitrobutane, nitrodichloropropane and others, as Well as the low molecular weight nitriles, such as acetonitrile. One of the preferred secondary solvents utilizable in admixture with a polyethylene and/or polypropylene glycol utilized as primary solvent constituents is water which is desirably `present in such a selective solvent composition in amounts sufficient to yield aqueous glycols containing from 2 to about 40% by weight of water.

In many cases it is particularly advantageous to vary the amount of secondary solvent (usually by increasing it) after the first extraction step and prior to or during vthe second extraction step,'wherein rich solvent` from the first extraction is contacted with the relatively volatile displacing agent herein designated as compound C. The extraction of high boiling feed stock mixtures with selective solvents may be eected at temperatures 'of from about 30 to about 200 C., depending upon the `type of feed stock, the composition of the solvent and other mutually operable factors. ,In the case of the aqueous glycols, particularly an aqueous mixture of `di ethylene and dipropylene glycols, the preferred extraction temperature is from about to about 175 C., the solvent being maintained in lliquid phase by the imposition of a superatmospheric pressure in the extraction zone, pressures up to about l5 atmospheres generally being sufficient for the maintenance of liquid phase conditions. The volume of solvent per volume of feed stock charged to the extraction zone depends upon the concentration of the polar or A component in the feed stock mixture and the temperature and compositionof the solvent, but generally volume ratios of solvent to feed stock of from about 1 to l to about 30 to 1 and preferably from about 3 to l to about 20 to 1 provide a suitable operating range of this factor for most feed stocks; however even higher ratios may be employed in the case of certain solvents of high selectivities and feed stocks containing a large proportion of organic polar component. The particular operating conditions essential for the recovery of the desired product are variables which must necessarily be determined on the basis of the particular feed stocks and in some instances higher temperatures may be required for the sole purpose of reducing the viscosity of the feed stock in order to permit adequate flow rates between the individual units of the process.

fn accordance with the flow of the present process, the extract or rich solvent phase formed in the solvent extraction zone is removed therefrom and contacted in a secondary contacting or extraction zone, referred to herein as a solute-exchange zone, with a polar organic compound C more volatile than the solvent or compound A in the extract phase whereby compound A derived from the feed stock is displaced therefrom with the preferentially soluble, lower molecular weight, organic compound C supplied to the solute exchange zone in excess of that required to displace compound A from the fat solvent. it is generally preferred, although not necessarily essential, that organic `compound C utilized in the solute exchange zone for preferential displacement of the extracted component from the fat solvent stream be a lower molecular weight, more volatile compound of the same class of compounds as compound A extracted by the solvent from the feed stock. Thus, in the recovery of a high molecular weight aromatic hydrocarbon, such as a polycyclic or alkyl-benzene hydrocarbon from non-aromatic hydrocarbons in admixture therewith, compound C utilized in the solute exchange zone for the purpose of displacing the high boiling extracted feed stock component A may be a low molecular weight aromatic compound such as benzene, toluene, a xylene, ethylbenzene, etc. or a mixture of such lower molecular weight aromatic hydrocarbons, or a naphtha containing these aromatic hydrocarbons. Similarly, in the extraction of a high molecular Weight fatty acid ester from a mixture of such esters of similar molecular weight, the compound C utilized for displacing the extracted ester from the fat solvent stream may be a lower molecular weight fatty acid ester, such as ethyl acetate, butyl formate, iso-propyl acetate etc. Although the particular compound C utilized to displace the extracted component from the fat solvent stream is desirably a compound of the same :general class of materials as the solute contained in the fat solvent ystream and is also preferably a compound preferentially dissolved by the solvent, these conditions are not necessarily essential to effect the displacement of the dissolved A compound from the fat solvent stream. Thus, the displacing compound C may be one which is merely soluble in the solvent but not necessarily preferentially soluble as compared to the feed stock-derived compound A dissolved in the solvent during the extraction stage of the process. For example, a polycyclic aromatic hydrocarbon of relatively high boiling point extracted byi the solvent in the extraction .stage bedisplaced-.withga generally less readily .extractedpolyolenic --or cycloolenic hydrocarbon fof lower molecular weight, such as heptadiene, methylcyclohexane, -etc.v In such instances, however, the displacing compound C .which is v.less preferentially soluble in the solvent than the-extractedcomponent A must generally ber-supplied to the secondary extraction column or solute exchange-:zone ingreatervolume ratio with respect to thel Afat solventl than in the -case of utilizing a more preferentially soluble organic compound of lower molecular weight than the extracted solute component, generallyin avolume ratio of displacing agent to fat solvent stream of Vfrom about O lnto l to about 30 to l volumes penvolume of" extract phase or Yfat solvent stream. It isgenerallygpreferred, however, to utilize an organic compound C of lower molecular weight which is preferentia'llyfl soluble in thesolvent as compared to the extracted component, although not necessarily of the same general ,class of `compounds as the solute component of the fat solvent stream, v suitable ow rates of the respective streams in such instances being from about 0.1 to l to about toil volumes of displacing agent to fat solvent Vstreamf A high molecular weight alkyl aromatic hydrocarbon, for example, such as dodecylbenzene, may be displaced from the fat solvent stream Vrecovered from the primary extraction zone with benzene, toluene or other alkyl aromatic hydrocarbon of shorterchain length than the dodecyl group, since alkyl aromatic hydrocarbons containing shorter/chain length alkyl groups are generally more soluble in the solvent than alkyl aromatic hydrocarbons containing long chain alkyl groups. In like manner, an unsaturated fatty acid ester, such as theglyceride ester of oleicacid is replaced from the fat solvent stream by contacting the fat solvent with a stream of a lower-boiling, more soluble ester, such as ethylbenzo'ate, thelatter being preferentially soluble in thejsolvent as compared to the oleic acid ester of glycerol.- Dependingupon the Yrelative'solvency in the selectivesolvent composition supplied to the primary extrac- -ton zonefthewquantity of 'compoundrC utilized as displacing-agent in the solute-exchange zone may vary over a relatively'wide range of ow rates, the volumetric Y ratioof displacingY agent C to fat solvent required to completely displace the extracted component A from the fat solventstream being `greater in the case of utilizing displacing 'agents which are less preferentially soluble than thefextracted component of the feed stock than whenjutilizing a displacing agent more readily dissolved in the ysolvent stream than the extracted feed stock component. d

VThe volume ratio of displacing agent or compound C to fat solvent supplied -to Vthe solute exchangezone is also dependent rupon the type of contactpmade between fthe=two streams Jduring the exchange. In general, the

volume ratio maybe considerably less when countercurrent flow between the Vdisplacing agent and the fat solventY stream is vemployed than in the case ofV merely mixing-the twor'uids or in co-current flow operations.Y

`For this reason',` countercurrent ow is generally pre- Y ferred,thedisplacing-agent, which is usually the phase of least'density, .'being introduced into the lowermost portion of the-solute exchange zone and allowed to ow upwardly therein against arcountercurr'entV stream of the fat solvent introduced into the top -of the solute exchange t zone, the' latter generally being in the form of an elon-V gated vertical column containing means for dispersing voneliqu'id, phase intlinelyV divided form-in aY streamY of fthe other liquid phase,` 'such as sieve deck plates, a suitable packing material, bubble caps and trays or other arrangementfto effect 'more intimate contact between the countercurrently flowing streams.

l As' -a 'result lof the Vdisplacing agent contacting the fat solvent-L stream `in thesolute-exchange zone,- compound A prefer 'tiallyV extracted -fromqft'he. feed stock 1in-the 'primaryfextaction zone is displaced therefrom with the S Y displacing agent of lower Amolecular weight, the primary extract phase thereafter containing dissolvedtherein the displacing agent as a secondary extract phase. The excess of compound C charged into the solute-exchange zone provides a stream containing the displaced feed stock component A as a distinct, separable phase which may be removed from the solute exchange zone, generally as a continuous stream when countercurrent ow operating conditions are provided. Since the displacing agent is selected from the organic compoundsof lower molecular weight, and hence of greater volatility than the extracted component of the feed stock,`the stream containing displaced compound A dissolved in the excess displacing agent, herein referred to as a secondary raffinate stream, may be charged into a distillation column wherein the two components comprising this stream, that is, the displacing 'agent or compound C and displaced feed stock component or compound A, are separated by distillation as distinct fractions having differing boiling points.

The operation Vof the present process as applied to a particular method of separation and to a particular feed stock comprising a preferred embodiment of the invention is further described in the accompanying diagram which illustrates, for the sake of convenience, the method of separation applied to a high boiling hydrocarbon feed stock containing naphthalene as component A to be recovered by means of the present .process and various aliphatic hydrocarbons including parafns as compound B, utilizing benzene as the displacing agent (compound C) in the solute exchange stage of the process flow. A -suitable selective solvent composition for a feed stock and displacing agent of this type is an aqueous solution of a mixture of diethylene and dipropylcne glycols, containing for example, from about 5% to about 15% vby Weight of water, from about 5 to about 40% by weight ofdiethylene glycol and from about to about 90% by weight of dipropylcne glycol. p

Referring to the accompanying diagram, a feed stock mixture containing an fextractable proportion of naphthalene and methylnaphthalenes, such asthe kerosene boiling range fraction of an aromatic-rich petroleum stock,.boiling, for example, from about 200 to about v275 C., is charged into the process ow from storage through line 1 and valve 2. The feed stock is transferred by. means of pump 3 into heater 4 containing a heating coll 5 wherein the naphthalene containing feed stock is heated to the desiredV extraction temperature generally feed stock, usually a compound which has a greater specific gravity than the hydrocarbon feed stock, is introduced into the top of the extraction zone through solvent recycle line 7, ythe solvent being recycled from subsequent stages of the process. In order to replace solvent losses in the system, if any, make-up solvent may be introduced into the dow through line S in amounts controlled by valve 9, line 8 connecting with solvent charge line 7. The relatively dense solvent lstream ows downwardly through extraction column 6 against a rising stream of feed stock introduced into the bottom of extraction zone d. lThe countercurrentrcontact between thefsolv'ent and feed stock selectively-removes the naphthalene component from the latter hydrocarbon mixture and rejects the parains,tolens, Vand1naphthenes, one or more of which maymalso be y-present'in the Vfeed stock mixture. The ,upwardly flowing, Yrejfzfc'tedv.feed stock components, comprising the primary raiiiate of the process is/remove'd 'from column '6 `through line 10 and-valve lfl im storage, to water washing equipment, `not shown, ior 1rem'oval of traces of solvent therefrom, or :for -ifurtlrer processing, if desired. The relatively dense solvent stream which lgravitates toward the lower :end of column 6 and which contains the naphthalene component of the feed stock dissolved therein is removed as fa fat fsolvent 'stream or extract phase from extraction zone `6 through line 12 in amounts controlled by valve .13. It is to be emphasized that although the solvent in most cases is relatively more dense than the feed stock mixture, extraction is equally operable for Ifeedstock mixtures which are more dense than the selective solvent composition, and in such cases the railinate .and extract streams and the feed stock and solvent ports of entry into zone 6 are reversed and are `on opposite ends of the column from those shown.

The fat solvent stream formed in primary extraction 4zone 6 is transferred by means vof pump 14 through line 15 into `the upper portion kof the solute exchange zone or secondary .extraction zone 16 wherein Lthe high boiling naphthalene component of Jthe fat solvent stream is ldisplaced with the more volatile benzene displacing agent which is introduced `into the lower portion of zone 16 through line t7. The benzene is recovered from subsequent stages or thezprocess, as yhereinafter described, `or

may be supplied from external sources entirelyror only in an amount suicient to :replace benzene Vlosses from `the system, the latter quantity being .introducedinto the process llow from benzene makeup through line .'18 .in an amount controlled by valve 19 which determines `the quantity of benzene charged into the benzene recycle line. 'Ehe dow of displacing agent and'fat solvent stream `in zone 16 is also desirably countercurrent to provide the most ecient method -for displacing the naphthalenev component of. the fat solvent with benzene. .Since the' fat solvent is generally the stream of greatest `specific gravity when utilizing a relatively dense solvent such -as an aqueous mixture of iglycols, this `stream is introduced into the top of solute exchange zone -16 and allowed to flow downwardly in countercurrent `relationship -with `the stream of benzene introduced into the bottom jportion of column 16. In one of the preferredembodiments of the invention, `the benzene is introduced in a volume the solute exchange column 16 through line 20 and valve 21 into a stripping zone such as distillation column 22 having a reboiler coil 23 in the lower portion of column 22 which supplies heat to the reboiling coil inside the column from a heat exchanger such asheatin'g unit 24 external to the column. The relatively volatile benzene component in the stream charged into distillationfzone 22 is removed overhead as a light fraction through Ivapor overhead line 25 containing valve 26,'-t'he benzene stream joining another stream of benzene recovered as vhereinafter described for recycle to the lower portion o'f, the solute exchange zone 16. The high boiling'naphthalene component charged into distillationzone 22 collects as a residue in the lower portion of columnv22 and is 4removed therefrom through line 28 in controlled amounts 'determined by valve 29 to'storage or to fui-'ther fractionating facilities to separate a naphthalene product of vgreater purity, if desired.

In many cases, as when `aqueousglycols are Jused Ias' Athe solvent, it will be desirable toinsertlwater washing facilities in line 20 (not shown) wherebyI residual fglycols may Vbe recoveredfrom the.secondaryrlratlinatelstream prior to distillation of thela'ttertin vcolun'ln222. 'Eheovater .washings containing vdissolved irecoveredsolvelnt,may -1 he charged to the soil-vent extraction zone, the solute fe change zone the .solvent stripper, Orthey :may he ser `,ara'tely distilled to lrecover solvent therefrom. In order yto lpromote the displacement of the dissolved `solute cornponent A such as the extracted naphthalene compound from the fat solvent stream, a ,stream of secondary solvent 4(such `as -water or the aqueous glycol stream recovered from the raliinate washing procedure) may r be `mixed with the primary extract phase or fat solvent stream before the latter enters the solute exchange zone. Alternatively, the fat solvent may be mixed in the upper portion of the zone with the additional secondary solvent charged to the top of the column, `For .this purpose., water ymay be introduced into column 16 through line 30 in amounts controlled by valve 31.

Referring to column 16, the fat solvent stream which llows countercurrently downward in solute exchange relationship with the benzene vstream introduced into the lower portion of column V16 through line 17 is removed fromzthe bottom of the solute exchange zone through line 32 in amounts controlled by valve 33 and transferred by means of pump 34 through line 35 into the upper portion of sol .vent `stripping zone 36 for the regeneration of a lean solvent recycle stream ,and for the recovery of the `benzene component therefrom. The fat solvent stream thus re moved from column 16 and lintroduced into stripper 36 contains onlybenzene dissolved in the solvent by virtue of having displaced thenaphthalene component from the fat solvent stream formed in the primary extraction stage-0f the process, provided that such replacement is efficient `to Vthe extent of having effected the quantitative removal of the uaphthalene component 'from the fat solvent during `its time of contact with the benzene in zone 16. In order to enhance the solubility of benzene in the solvent relative toV4 that of lthe napbthalenes, and thereby-permit the displacement of the naphthalene component from the fat solvent stream, the temperature or the water content of the latter stream may be adjusted prior to their introduc `tion into zone lr6, as indicated, by water introduced into zone therein through line 3l).

Solvent stripping column 36 i-s operated under conditions suitable `to effect the substantially complete removal of benzene from the fat solvent stream charged thereto and thereby regenerate a lean solvent substantially free of Vhydrocarbon solute components, desirably as free of solute as possible to increase its solvency in the primary extraction zone 6. Solvent stripping Zone 36 is desirably provided witha reboiling coil, such as reboiler 37 in its lower portion, :the lreooiler being supplied with heat in heat exchanger `38. Inorder to accomplish as complete removal of benzenevfrom the fat solvent stream as possible, column .36 may he operated at a reduced pressure relative to zone I6 and 16,V and a stripping agent such as steam may be in- Atroduced into the lower portion ofzone 36, or other suie able means for effecting substantially complete vaporiza- -tion of Vthe benzene from the fat `solvent stream may be provided in zone 36. lfV steam stripping is employed, the condensate water may be employed for scrubbing or `waterfwashingthe solute in the line 20 stream (as previously described) before being returned to the stripper column v36. The benzene stripped from the fat solvent is removed as an overhead fraction from column 36 through line 59, and discharged in amounts controlled by valve di) into benzene recycle `line 27, the benzene being transferred into linelfli through valve 4l by means of pump 42. lf heated prior to Vits recycle into columnl, a suitable heater:- mchange unit, not illustrated, is incorporated intov there oyclegflow line. The stripped glycol solvent from which the hydrocarbon solute components have been removed is withdrawn from the lower portion of column 36 through linesd, through valve tft and transrerred by means of .pump't45 intoglycol reci/Gle line 7 which dischargesthe jrecycledfleansolvent into the top of ,solvent-*extraction @Omen `in. accordance-with the processilowY heretofore de HOneof the preferred methods of operation, generally resulting in the most etcient process and resulting in the least consumption of heating utilities Vin the combined flow is provided when solvent extraction zone 6, solute exchange zone 16 and solvent stripper 36 are opera-ted at substantially the same temperature, stripping being etfected in Vzone 36 by reduction of the pressure on the fat solvent stream charged thereto, for example, to atmospheric pressure, and zones 6 andv 16 being operated at superatmos- -pheric pressures in order to maintain liquid phase therein.

The present invention is further illustrated with respect 'to-some' of itspreferred embodiments in the following examples whiclrare introduced merely for the purpose of illustration and not with the intention of unduly limiting the scope of the invention in accordance therewith.

Example I 4Naphthalene is recovered in substantially pure form utilizing an extraction procedure similar in its essential respects to the flow described in the above accompanying diagram. A hydrocarbon feed stock comprising the gas oil fraction` of a catalytically cracked Mid-Continent petroleum crude, boiling in the range of from 200 to about 230 C. and containing 13% by weight of naphtlialene is charged into the bottom of a sieve-deck extraction column containing 45 plates while an aqueous diethylene glycol solvent containing aboutr7.5r% water is charged onto the top tray of the column i. e. on plate 1. The ow rates of the gas Voil fraction and solvent are adjusted to provide a solvent to feed stock ratio of V10/1. A' raffinate phase containing less than 0.3% by weight of ar'omatic'components is removed from the top of the extraction column, an extract phase or fat solvent stream containing dissolved naph-thalene is removed from the bot tom of the column and charged into the top of the solutecxchange column, and a benzene stream is charged into the bottom of the column. The latter solute-exchange column is a quartz'chip-packed contacting zone maintained at the above specified temperature of 135 C. and at a pressure of 90 lbs/in.2 gage. The benzene rate of vtiow is sufiicient to provide a benzene to fat solvent ratio ot' 2/1 in the solute-exchange column. A secondary ratlinate stream comprising excess benzene, above the quantity required to displace naphthalene from the fat solvent and containing dissolved therein the displaced Vnaphthalene formerly in the primary extract phase, is removed from. the top of the solute-exchange column and diverted to a fractional distillation column for the separation of the light benzene displacing agent from the higher boiling naphthalene product extracted from the feed stock. The benzene is taken overhead from the column and recycled to the solute-exchange column. A high boiling bottoms residue containing 98.5% naphthalene is removed from the bottom of the still; the yield of crude naphthalene thus recovered represents from about 12% to about 127.8% by weight of the initial gas oil charged to the process.

TheA secondary fat solvent stream removed from the bottornV of the solute-exchange column is charged into a solvent stripping column wherein the pressure on the fat solvent stream' is reduced in stages from 90 lbs./in.2 to atmospheric pressure, In the rst stage wherein the pressureis reduced to lb's./in.2, a benzene-containing fraction, withy some water, is `distilled overhead. In the second stage pressure reduction, a fraction'comprising benzene, water and a small quantity of solvent is distilled from the column as a side stream. The overhead fraction is condensed and the benzene recycled to the solute-exchange column. Superheated steam at a temperature of '150 C. is injected into the fat solvent residue in the bottom of the column, the residue also being heated with alreboiler coil through which heated diphenyl oxide is circulated." A lower side-cut fraction removed at substantially atmospheric pressure, containing a small amount of residual naphthalcne, benzene and water is removed from the stripping column, condensed, and run into a receiver vessel. The upper hydrocarbon layer recov ered from the lower side-cutV fraction is decanted from the water and' recycled to the feed stock charge line into the solute exchange zone. Both water condensate streams 'may bel recycled to the solvent extraction zone, to the solute exchange zone, or to the solvent stripper, or may .be used to scrub glycol from the secondary solute (benzene) solution of naphthalene prior to distillation of this stream, and kthen recycled to one or more of the zones mentioned.

The naphthalene-containing residue of the benzene stripping column is redistilled to separate a residue containing 99.+ by weight of naphthalene.

Example II The alkylate product of a sulfuric acid-catalyzed alkylation of benzene with a dodecylene-containing cracked naphtha fraction contains about 8% by volume of olenic hydrocarbons (presumably polymers) which cannot be removed from the desired benzene alkylate components by fractional distillation because lof the close proximity of the boiling points of the olenic hydrocarbon contaminants to the desired dodecylbenzene product. The crude alkylate as separated from the products of the alkylation reaction has a bromine number of 5, indicating the substantially olefinic character of the alkylate When sulfonated to produce an alkylarylsulfonate type of detergent, the olefin-contaminated product produces a neutralized sulfonate which is dark-colored and has a detergency substantially less than the detergent prepared from a specially puried dodecylbenzene alkylate.

The above-referred to contaminated alkylate is utilized as feed into a countercurrent liquid-liquid extraction column to separate a more desirable alkylate product for detergent manufacture therefrom free of contaminating hydrocarbons. The extraction conditions of temperature, pressure, solvent flow rate and solvent composition utilized in the process are essentially similar to the extraction conditions described in Example I, above, except that toluene is utilized as the solute-exchange displacing agent. The dodecylbenzene product recovered from the toluene component of the secondary raflnate stream in the toluene stripping column following the solute-exchange operation is substantially pure deoleiinized aromatic (bromine No. 0.2) and when sulfonated, followed by neutralization of the resulting alkylarylsulfonic acid with caustic soda, the detergent product is white and its detergency equal to the specially purified sample of dodecylbenzene sulfonate.

l claim as my invention:

-l. A process for separating apolycyclic aromatic hydrocarbon from a non-aromatic hydrocarbon of approximately the same volatility which comprises contacting a mixture of said aromatic and non-aromatic hydrocarbons` at a temperature of from about 75 to about 200 C. with a solvent comprising an aqueous solution of at least one polyoxyalkylene'glycol capable of selectively dissolving said polycyclic aromatic hydrocarbon, said hydrocarbons beingrhigher boiling than said solvent, separating a resulting Vfat solvent stream comprising said solvent and containing `dissolved Itherein said polycyclic aromatic hydrocarbon from a resulting primary ranate stream comprising a non-aromatic hydrocarbon component of said mixture, separately contacting said fat solvent stream with a monocyclic aromatic hydrocarbon of greater volatility than said polycyclic aromatic hydrocarbon, separating a resulting secondary raiiinate stream comprising said polycyclic aromatic hydrocarbon dissolved in an excess of said monocyclic aromatic hydrocarbon from a secondary fat solvent stream, subjecting s'aid secondary fat solvent stream to'distillation, separately recovering regenerated solvent and a )monocyclic aromatic hydrocarbon stream, recycling said`regenerated solvent to said first-mentioned contacting step and said monocyclic aromatic hydrocarbon to said last-mentioned contacting step, and separately Y recovering monocyclic and polycyclic aromatic hydrocarbons from said secondary rainate stream.

2. A process -for separating a polycyclic aromatic hydrocarbon from a non-aromatic hydrocarbon of approximately the same volatility which comprises contacting a mixture of said aromatic and non-aromatic hydrocarbons at a temperature of from about 75 to about 200 C. with a solvent comprising an aqueous solution of at least one polyoxyalkylene glycol capable of selectively dissolving said polycyclic aromatic hydrocarbon, said hydrocarbons being higher boiling than said solvent, separating a resulting fat solvent stream comprising said solvent and containing dissolved therein said polycyclic aromatic hydrocarbon from a resulting primary raffinate stream comprising a non-aromatic hydrocarbon component of said mixture, separately contacting said fat solvent stream with a monocyclic aromatic hydrocarbon of greater volatility than said polycyclic aromatic hydrocarbon, separating a resulting secondary raimate stream comprising said polycyclic aromatic hydrocarbon dissolved in an excess of said monocyclic aromatic hydrocarbon from a secondary fat solvent stream, subjecting said secondary fat solvent stream to distillation, separately recovering regenerated solvent and a monocyclic aromatic hydrocarbon stream, recycling said regenerated solvent to said rst-mentioned contacting step and said monocyclic aromatic hydrocarbon to said last-mentioned contacting step, subjecting said secondary rainate stream to distillation and separately recovering monocyclic and polycyclic aromatic hydrocarbons therefrom. Y

3. A process for `separating a polycyclic aromatic hydrocarbon from a non-aromatic hydrocarbon of approximately the same volatility which comprises contacting a mixture of said aromatic and non-aromatic hydrocarbons at a temperature of from about to about 200 C. with a solvent comprising an aqueous solution of at least one polyoxyalkylene glycol capable of selectively dissolving said polycyclic aromatic hydrocarbon, said hydrocarbons being higher boiling than said solvent, separating a resulting fat solvent stream comprising said solvent and containing dissolved therein said polycyclic aromatic hydrocarbon from a resulting primary rainate stream comprising a non-aromatic hydrocarbon component of said mixture, separately contacting said fat solvent stream with benzene, separating a resulting secondary rafnate stream comprising said polycyclic aromatic hydrocarbon dissolved in an excess of said benzene from a secondary extract stream, subjecting said secondary extract stream to distillation, separately recovering regenerated solvent and a benzene stream, recycling said regenerated solvent to said rst-mentioned contacting step and said benzene to said last-mentioned contacting step, subjecting said secondary raiinate stream to distillation and separately recovering therefrom benzene and said polycyclic aromatic hydrocarbon.

4. The process of claim 3, further characterized in that said polycyclic aromatic hydrocarbon is naphthalene.

References Cited in the tile of this patent UNITED STATES PATENTS Re. 19,763 Tuttle Nov. 19, 1935 2,114,524 Egli Apr. 19, 1938 2,176,396 Fenske et al. Oct. 17, 1939 2,261,799 Franklin c Nov. 4, 1941 2,414,252 Ashburn Jan. 14, 1947 2,568,176 Vriens et al. Sept. 18, 1951 2,633,448 Neuworth Mar. 31, 1953 

1. A PROCESS FOR SEPARATING A POLYCYCLIC AROMATIC HYDROCARBON FROM A NON-AROMATIC HYDROCARBON OF APPROXIMATELY OF SAID AROMATIC AND NON-AROMATIC HYDROCARBONS MIXTURE OF SAID AROMATIC AND NON-AROMATIC HYDROCARBONS AT A TEMPERATURE OF FROM ABOUT 75* TO ABOUT 200*C. WITH A SOLVENT COMPRISING AN AQUEOUS SOLUTION OF AT LEAST ONE POLYOXYALKYLENE GLYCOL CAPABLE OF SELECTIVELY DISSOLVING SAID POLYCYCLIC AROMATIC HYDROCARBON, SAID HYDROCARBONS BEING HIGHER BOILING THAN SAID SOLVENT, SEPARATING A RESULTING FAT SOLVENT STREAM COMPRISING SAID SOLVENT AND CONTAINING DISSOLVED STREAM COMPRISING SAID SOLVENT AND CONCARBON FROM A RESULTING PRIMARY RAFFINATE STREAM COMPRISING A NON-AROMATIC HYDROCARBON COMPONENT OF SAID MIXTURE, SEPARATELY CONTACTING SAID FAT SOLVENT STREAM WITH A MONOCYCLIC AROMATIC HYDROCARBON OF GREATER VOLATILITY THAN SAID POLYCYCLIC AROMATIC HYDROCARBON, SEPARATING A RESULTING SECONDARY RAFFINATE STREAM COMPRISING SAID POLYCYCLIC AROMATIC HYDROCARBON DISSOLVED IN AN EXCESS OF SAID MONOCYCLIC AROMATIC HYDROCARBON FROM A SECONDARY FAT SOLVENT STREAM, SUBJECTING SAID SECONDARY FAT SOLVENT STREAM TO DISTILLATION, SEPARATELY RECOVERING REGENERATED SOLVENT AND A MONOCYCLIC AROMATIC HYDROCARBON STREAM, RECYCLING SAID REGENERATED SOLVENT TO SAID FIRST-MENTIONED CONTACTING STEP AND SAID MONOCYCLIC AROMATIC HYDROCARBON TO SAID LAST-MENTIONED CONTACTING STEP, AND SEPARATELY RECOVERING MONOCYCLIC AND POLYCYCLIC AROMATIC HYDROCARBONS FROM SAID SECONDARY RAFFINATE STREAM. 